1. Field of the Invention
The present invention relates to novel fused-benzene derivatives, their salts and compositions, intermediates, a process for producing them, and their use as herbicides.
2. Description of the Related Art
U.S. Pat. No. 4,859,229 discloses the herbicidal utility of uracil derivatives, in which the phenyl ring of the described compounds did not have any 2,6-disubsutitutions. Recently WO98/38188 and WO99/31091 disclosed benzoxazole and benzothiazole derivatives which have potent herbicidal activity in preemergence and postemergence applications.
The formula is;
wherein; 
Q is uracil and D is either oxygen or sulfur. U.S. Pat. No. 5,169,431 disclosed benzofuran or benzothiophene type derivatives with Q as uracil and D is carbon. WO97/29105 disclosed benzofuran derivatives with Q as uracil and D is oxygen. WO93/14073 disclosed substituted dihydrobenzofuran type compounds with Q as uracil or triazine derivatives and D is carbon. U.S. Pat. No. 5,521,147 disclosed dihydrobenzofuran, dihydrobenzopyran and dihydrobenzofuran-3-one type derivatives with Q as uracil and D or M is oxygen. EP. 0,271,170 disclosed dihydrobenzofuran and dihydrobenzopyran derivatives where Q is many kinds of heterocycles and D or M is carbon. WO95/33746 disclosed cyclic sulfonamide derivatives where Q is many kinds of heterocycles including uracil and D is carbon. U.S. Pat. No. 5,346,881 disclosed benzodioxin or benzodioxole derivatives where Q is uracil, M is oxygen. JP 09301973 disclosed 2H-chromene type derivatives with Q is many kinds of heterocycles including uracil and M is oxygen. WO97/12886 disclosed benzisoxazole or benzisoxazolidinone derivatives where Q is many kinds of heterocycles including uracil and D is oxygen.
WO97/42188 disclosed indole type derivatives with Q as uracil and D or U isnitrogen. Despite the broad coverage of these patents, the general structure of the present invention has not been described.
The specific fused-benzene compounds of the formula (Ia) and (Ib) mentioned below are novel and can be used to effectively control a variety of broad or grassy leaf plant species.
The invention delineates a method for the control of undesired vegetation in a plantation crop by the application to the locus of the crop an effective amount of a compound described herein. The present application describes certain herbicidal fused benzene derivatives of the formula (Ia) and (Ib) including all geometric, tautomeric and stereo isomers, and their salts, as well as compositions containing them and methods of preparation for these compounds. (Ia) (Ib) 
in which
X, Y are independent of each other and are represented by hydrogen, halogen, cyano, nitro, (C1-4)alkyl, (C1-4)alkoxy, (C1-4)haloalkyl or (C1-4)haloalkoxy;
A is oxygen, nitrogen, NR1, CR3, CR3R4, S(O)n*, C(xe2x95x90O), C(xe2x95x90S) or C(xe2x95x90NR1);
D is nitrogen or NR2;
M is CR5, CR5R6, nitrogen, NR2, S(O)n*, C(xe2x95x90O), C(xe2x95x90S) or C(xe2x95x90NR2);
When A is oxygen, M is nitrogen, NR2, S(O)n*, C(xe2x95x90O), C(xe2x95x90S) or C(xe2x95x90NR2);
E and L are independent of each other and may be selected from CR7, CR8, CR7R8, oxygen, nitrogen, NR7, S(O)n*, C(xe2x95x90O), C(xe2x95x90S), C(xe2x95x90NR7) or CNR7R8;
U is CR9, oxygen, nitrogen, NR2, S(O)n*, C(xe2x95x90O), C(xe2x95x90S) or C(xe2x95x90NR2);
When U is CR9, E is nitrogen;
R1 and R2 are independent of each other and may be selected from the group consisting of hydrogen, (C1-6)alkyl, (C2-6)alkenyl, (C2-6)alkynyl, (C1-6)alkylcarbonyl, (C-6)cycloalkylcarbonyl, (C1-6)haloalkylcarbonyl, (C1-6)alkoxycarbonyl, arylcarbonyl and heteroarylcarbonyl,
where any of these groups may be optionally substituted with one or more of the following groups consisting of halogen, hydroxy, cyano, nitro, amino, caboxyl, (C1-6)alkyl, (C1-6)haloalkyl, (C1-6)alkylcarbonyl, (C1-6)alkylcarbonyloxy, (C1-6)haloalkylcarbonyl, (C1-6)haloalkylcarbonyloxy, (C1-6)alkoxy, (C1-6)alkoxycarbonyl, aminocarbonyl, (C1-6)alkylaminocarbonyl, (C1-6)haloalkoxy, (C1-6)haloalkoxycarbonyl, (C1-6)alkylsulfonyl, (C1-6)haloalkylsulfonyl, aryl, heteroaryl and (C3-7)cycloalkyl, R3, R4, R5, R6, R7, R8 and R9 are independent of each other and may be selected from the group consisting of hydrogen, halogen, hydroxy, mercapto, amino, cyano, nitro, (C1-6)alkyl, (C1-6)haloalkyl, (C1-6)alkoxy, (C1-6)haloalkoxy, (C1-6)alkoxyalkyl, (C2-6)alkynyl ,(C2-6)alkenyl, aryl, heteroaryl, aryloxy, heteroaryloxy, (C3-6)cycloalkyl, (C3-6)cyclocarbonyl, carboxy, (C1-6)alkylcarbonyl, arylcarbonyl, (C1-3)haloalkylcarbonyl, (C1-6)alkylcarbonyloxy, (C1-6)haloalkylcarbonyloxy, (C1-6)alkoxycarbonyl, (C1-6)haloalkoxycarbonyl, (C1-6)alkylthiocarbonyl, (C1-6)haloalkylthiocarbonyl, (C1-6)alkoxythiocarbonyl, (C1-6)haloalkoxythiocarbonyl, (C1-6)alkylamino, arylsulfonylamino, arylamino, (C1-6)alkylthio, arylthio, (C2-6)alkenylthio, (C2-6)alkynylthio, (C1-6)alkylsulfinyl, (C2-6)alkenylsulfinyl, (C2-6)alkynylsulfinyl, (C1-6)alkylsulfonyl, (C2-6)alkenylsulfonyl, (C2-6)alkynylsulfonyl, arylsulfonyl, where any of these groups may be optionally substituted with one or one more of the following group consisting of halogen, hydroxy, mercapto, cyano, nitro, amino, caboxy, (C1-6)alkyl, (C1-6)haloalkyl, (C1-6)alkylcarbonyl, (C1-6)alkylcarbonyloxy, (C1-6)haloalkylcarbonyl, (C1-6)haloalkylcarbonyloxy, (C1-6)alkoxy, (C1-6)alkoxycarbonyl, aminocarbonyl, (C1-6)alkylaminocarbonyl, (C1-6)haloalkoxy, (C1-6)haloalkoxycarbonyl, (C1-6)alkylsulfonyl, (C1-6)haloalkylsulfonyl, aryl, haloaryl, alkoxyaryl, aryoxy, arylthio, haloaryloxy, heteroaryl, heteroaryloxy and (C3-7)cycloalkyl;
n* is represent an integer from 0 to 2;
Q is selected from; 
xe2x80x83wherein
A1 and A2 are independently oxygen or sulfur;
R10 is hydrogen, halogen, cyano, nitro, formyl, (C1-4)alkyl, (C1-4)haloalkyl, amino, (C1-4)alkylamino, (C1-4)haloalkylamino, (C1-4)alkoxyamino, (C1-4)haloalkoxyamino, (C1-4)alkylcarbonyl, (C1-4)haloalkylcarbonyl, (C1-4)haloalkoxycarbonyl, (C1-4)alkylcabonylamino, (C1-4)haloalkylcarbonylamino, (C1-4)alkoxycarbonylamino, (C1-4)haloalkoxycarbonylamino, (C1-6)alkoxyalkyl, (C1-6)haloalkoxyalkyl, (C1-6)alkylthio, (C1-4)haloalkylthio, (C2-6)alkenyl, (C2-4)haloalkenyl, (C2-6)alkynyl or (C2-6)haloalkynyl;
R11, R12 and R18 are independent of each other and may be selected from the group consisting of hydrogen, halogen, cyano, (1-4)alkyl, (1-4)haloalkyl, (C1-4)alkoxy, (C1-4)haloalkoxy, (C2-6)alkenyl, (C2-6)haloalkenyl, hydroxy or amino which may be optionally substituted with (C1-4)alkyl and (C1-4)haloalkyl;
R13 and R14 are independent of each other and may be selected from the group consisting of hydrogen, halogen, (C1-3)alkyl, (C1-3)haloalkyl, hydroxy, (C1-3)alkoxy, (C1-3)haloalkoxy, cyano, nitro, amino or (C1-6)alkylamino,
When R13 and R14 are taken together with the atoms to which they are attached, they represent a three to seven membered substituted or unsubstituted ring optionally containing oxygen, S(O)n*** or nitrogen with following optional substitutions, one to three halogen, cyano, nitro, hydroxy, amino, carbonyl, (C1-6)alkyl, (C1-6)haloalkyl, (C1-6)alkylcarbonyl, (C1-6)alkylcarbonyloxy, (C1-6)haloalkylcarbonyl, (C1-6)haloalkylcarbonyloxy, (C1-6)alkoxy, (C1-6)alkoxycarbonyl, aminocarbonyl, (C1-6)alkylaminocarbonyl, (C1-6)haloalkoxy, (C1-6)haloalkoxycarbonyl, (C1-6)alkylsulfonyl. (C1-6)haloalkylsulfonyl, aryl, heteroaryl or (C3-7)cycloalkyl;
G is nitrogen or CR16,
Gxe2x80x2 is NR15, oxygen, S(O)n*** or CR16R17,
Gxe2x80x3 is nitrogen, CR16, NR15 oxygen, S(O)n. . . or CR16R17 
R15 may be selected from the group consisting of hydrogen, (C1-6)alkyl, (C1-6)alkylcarbonyl, (C1-6)haloalkylcarbonyl, arylcarbonyl and heteroarylcarbonyl; where any of these groups may be optionally substituted with one or more of the following groups consisting of halogen, hydroxy, cyano, nitro, amino, caboxyl, (C1-6)alkyl, (C1-6)haloalkyl, (C1-6)alkylcarbonyl, (C1-6)alkylcarbonyloxy, (C1-6)haloalkylcarbonyl, (C1-6)haloalkylcarbonyloxy, (C1-6)alkoxy, (C1-6)alkoxycarbonyl, aminocarbonyl, (C1-6)alkylaminocarbonyl, (C1-6)haloalkoxy, (C1-6)haloalkoxycarbonyl, (C1-6)alkylsulfonyl, (C1-6)haloalkylsulfonyl, aryl, heteroaryl and (C3-7)cycloalkyl
R16 and R17 are independent of each other and may be selected from the group consisting of hydrogen, halogen, hydroxy, mercapto, amino, cyano, (C1-6)alkyl, (C1-6)haloalkyl, (C1-6)alkoxy,(C1-6)haloalkoxy, (C1-6)alkoxyalkyl, (C2-6)alkynyl, (C2-6)alkenyl, aryl, heteroaryl, aryloxy, heteroaryloxy, (C3-6)cycloalkyl, (C3-6)cyclocarbonyl, carboxy, (C1-6)alkylcarbonyl, arylcarbonyl, (C1-3)haloalkylcarbonyl, (C1-6)alkylcarbonyloxy, (C1-6)haloalkylcarbonyloxy, (C1-6)alkoxycarbonyl, (C1-6)haloalkoxycarbonyl, (C1-6)alkylthiocarbonyl, (C1-6)haloalkylthiocarbonyl, (C1-6)alkoxythiocarbonyl, (C1-6)haloalkoxythiocarbonyl,(C1-6)alkylamino, arylsulfonylamino, arylamino, (C1-3)alkylthio, arylthio, (C2-6)alkenylthio, (C2-6)alkynylthio, (C1-6)alkylsulfinyl, (C2-6)alkenylsulfinyl, (C2-6)alkynylsulfinyl, (C1-6)alkylsulfonyl, (C2-6)alkenylsulfonyl, (C2-6)alkynylsulfonyl, arylsulfonyl, where any of these groups may be optionally substituted with one or one more of the following group consisting of halogen, hydroxy, mercapto, cyano, nitro, amino, caboxyl, (C1-6)alkyl, (C1-6)haloalkyl, (C1-6)alkylcarbonyl, (C1-6)alkylcarbonyloxy, (C1-6)haloalkylcarbonyl, (C1-6)haloalkylcarbonyloxy, (C1-6)alkoxy, (C1-6)alkoxycarbonyl, aminocarbonyl, (C1-6)alkylaminocarbonyl, (C1-6)haloalkoxy, (C1-6)haloalkoxycarbonyl, (C1-6)alkylsulfonyl, (C1-6)haloalkylsulfonyl, aryl, heteroaryl and (C3-7)cycloalkyl;
n and m are independent of each other and represent an integer from 0 to 2; provided that m+n is 2, 3 or 4,
n** is 0 or 1,
n*** is represent an integer from 0 to 2,
When Q is Q1, Q3, Q4, Q13, Q18 or Q19, structure (Ib) is excluded,
When Q is Q7, U is CR9, nitrogen, NR2, C(xe2x95x90O), C(xe2x95x90S) or C(xe2x95x90NR2),
Preferred compounds for the reasons of greater herbicidal efficacy are represented by formula (Ia) and (Ib) where
X, Y are independent of each other and are represented by hydrogen, halogen or cyano;
A is oxygen, nitrogen, NR1;
D is nitrogen or NR2;
M is nitrogen or NR2,
E and L are independent of each other and may be selected from CR7, CR8, CR7R8, oxygen, nitrogen, S(O)n*, C(xe2x95x90O), C(xe2x95x90S), C(xe2x95x90NR7) or CNR7R8;
U is oxygen, nitrogen, NR2 or S(O)n*;
R1 and R2 are independently of each other and may be selected from the group consisting of hydrogen, (C1-6)alkyl, (C2-6)alkenyl, (C2-6)alkynyl, (C1-6)alkylcarbonyl, (C-6)cycloalkylcarbonyl, (C1-6)haloalkylcarbonyl, arylcarbonyl and heteroarylcarbonyl,
where any of these groups may be optionally substituted with one or more of the following groups consisting of halogen, hydroxy, mercapto, cyano, nitro, amino, caboxyl, (C1-6)alkyl, (C1-6)haloalkyl, (C1-6)alkylcarbonyl, (C1-6)alkylcarbonyloxy, (C1-6)haloalkylcarbonyl, (C1-6)haloalkylcarbonyloxy, (C1-6)alkoxy, (C1-6)alkoxycarbonyl, aminocarbonyl, (C1-6)alkylaminocarbonyl, (C1-6)haloalkoxy, (C1-6)haloalkoxycarbonyl, (C1-6)alkylsulfonyl, (C1-6)haloalkylsulfonyl, aryl, haloaryl, alkoxyaryl, heteroaryl and (C3-7)cycloalkyl;
R3, R4, R5, R6, R7, R8 and R9 are independent of each other and may be selected from the group consisting of hydrogen, halogen, hydroxy, mercapto, amino, cyano, (C1-6)alkyl, (C1-6)haloalkyl, (C1-6)alkoxy, (C1-6)haloalkoxy, (C1-6)alkoxyalkyl, (C2-6)alkynyl , (C2-6)alkenyl, aryl, heteroaryl, aryloxy, heteroaryloxy, (C3-6)cycloalkyl, carboxy, (C1-6)alkylcarbonyl, arylcarbonyl, (C1-3)haloalkylcarbonyl, (C1-6)alkylcarbonyloxy, (C1-6)haloalkylcarbonyloxy, (C1-6)alkoxycarbonyl , (C1-6)haloalkoxycarbonyl, (C1-6)alkylthiocarbonyl, (C1-6)haloalkylthiocarbonyl, (C1-6)alkoxythiocarbonyl, (C1-6)haloalkoxythiocarbonyl, (C1-6)alkylamino, arylsulfonylamino, arylamino, (C1-3)alkylthio, arylthio, (C2-6)alkenylthio, (C2-6)alkynylthio, (C1)alkylsulfinyl, (C2-6)alkenylsulfinyl, (C2-6)alkynylsulfinyl, (C1-6)alkylsulfonyl, (C2-6)alkenylsulfonyl, (C2-6)alkynylsulfonyl, arylsulfonyl, where any of these groups may be non-substituted or substituted with any of the functional groups represented by one more of the following halogen, hydroxy, cyano, nitro, amino, caboxyl, (C1-6)alkyl, (C1-6)haloalkyl, (C1-6)alkylcarbonyl, (C1-6)alkylcarbonyloxy, (C1-6)haloalkylcarbonyl, (C1-6)haloalkylcarbonyloxy, (C1-6)alkoxy, (C1-6)alkoxycarbonyl, aminocarbonyl, (C1-6)alkylaminocarbonyl, (C1-6)haloalkoxy, (C1-6)haloalkoxycarbonyl, (C1-6)alkylsulfonyl, (C1-6)haloalkylsulfonyl, aryl, aryloxy, heteroaryl heteroaryloxy and (C3-7)cycloalkyl,
n* is represent an integer from 0 to 2,
When Q is Q1 or Q3 stricture (Ib) is excluded,
When Q is Q7, U is nitrogen or NR2,
Q is selected from Q1, Q2, Q3, Q7, Q9, Q10, Q16 or Q17,
wherein
A1 and A2 are independently oxygen or sulfur,
R10 is (C1-3)alkyl, (C1-3)haloalkyl or amino
R11, R12 are independent of each other and may be selected from the group consisting of hydrogen, halogen, cyano, (C1-4)alkyl, (C1-4)haloalkyl, (C1-4)alkoxy, (C1-4)haloalkoxy, (C2-6)alkenyl, (C2-4)haloalkenyl, hydroxy or amino which may be substituted with (C1-4)alkyl or (C1-4)haloalkyl;
R13 and R14 are independently of each other and may be selected from the group consisting of hydrogen, halogen, (C1-3)alkyl, (C1-3)haloalkyl, hydroxy, (C1-3)alkoxy, (C1-3)haloalkoxy, cyano, nitro, amino and (C1-6)alkylamino;
G is nitrogen or CR16,;
Gxe2x80x2 is NR15, oxygen, S(O)n*** or CR16R17,
R,5 may be selected from the group consisting of hydrogen, (C1-6)alkyl, (C1-6)alkylcarbonyl, (C1-6)haloalkylcarbonyl, arylcarbonyl and heteroarylcarbonyl,
R16 and R17 are independent of each other and may be selected from the group consisting of hydrogen, halogen, hydroxy, mercapto, amino, cyano, (C1-6)alkyl, (C1-6)haloalkyl, (C1-6)alkoxy,(C1-6)haloalkoxy, (C1-6)alkoxyalkyl, (C2-6)alkynyl, (C2-6)alkenyl, aryl, heteroaryl, aryloxy, heteroaryloxy, (C3-6)cycloalkyl, carboxy, (C1-6)alkylcarbonyl, arylcarbonyl, (C1-3)haloalkylcarbonyl, (C1-6)alkylcarbonyloxy, (C1-6)haloalkylcarbonyloxy, (C1-6)alkoxycarbonyl, (C1-6)haloalkoxycarbonyl, (C1-6)alkylthiocarbonyl, (C1-6)haloalkylthiocarbonyl, (C1-6)alkoxythiocarbonyl, (C1-6)haloalkoxythiocarbonyl, (C1-6)alkylamino, arylsulfonylamino, arylamino, (C1-3)alkylthio, arylthio, (C2-6)alkenylthio, (C2-6)alkynylthio, (C1-6)alkylsulfinyl, (C2-6)alkenylsulfinyl, (C2-6)alkynylsulfinyl, (C1-6)alkylsulfonyl, (C2-6)alkenylsulfonyl, (C2-6)alkynylsulfonyl, arylsulfonyl, where any of these groups may be non-substituted or substituted with any of the functional groups represented by one more of the following halogen, hydroxy, cyano, nitro, amino, caboxyl, (C1-6)alkyl, (C1-6)haloalkyl, (C1-6)alkylcarbonyl, (C1-6)alkylcarbonyloxy, (C1-6)haloalkylcarbonyl, (C1-6)haloalkylcarbonyloxy, (C1-6)alkoxy, (C1-6)alkoxycarbonyl, aminocarbonyl, (C1-6)alkylaminocarbonyl, (1-6)haloalkoxy, (C1-6)haloalkoxycarbonyl, (C1-6)alkylsulfonyl, (C1-6)haloalkylsulfonyl, aryl, heteroaryl and (C3-7)cycloalkyl
n and m are independent of each other and represent an integer from 0 to 2; provided that m+n=2 or 3;
n** is 0 or 1;
n*** is represent an integer from 0 to 2.
Certain compounds of present invention are novel. These are represented by the following formula. 
in which
X is hydrogen or halogen;
Y is halogen, cyano, nitro, (C1-3)haloalkyl, or (C1-3)alkoxyalkyl;
Q is O1, Q2, Q3, Q7, Q9, Q10, Q16 or Q17;
R19 is hydrogen, (C1-6)alkyl, (C1-6)alkylcarbonyl, (C1-6)haloalkylcarbonyl, arylcarbonyl, heteroarylcarbonyl;
where any of these groups may be optionally substituted with one or more of the following groups consisting of halogen, hydroxy, cyano, nitro, amino, caboxyl, (C1-6)alkyl, (C1-6)haloalkyl, (C1-6)alkylcarbonyl, (C1-6)alkylcarbonyloxy, (C1-6)haloalkylcarbonyl, (C1-6)haloalkylcarbonyloxy, (C1-6)alkoxy, (C1-6)alkoxycarbonyl, aminocarbonyl, (C1-6)alkylaminocarbonyl, (C1-6)haloalkoxy, (C1-6)haloalkoxycarbonyl, (C1-6)alkylsulfonyl, (C1-6)haloalkylsulfonyl, aryl, heteroaryl and (C3-7)cycloalkyl;
R20 is selected from the group consisting of hydrogen, halogen, hydroxy, mercapto, amino, cyano, (C1-6)alkyl, (C1-6)haloalkyl, (C1-6)alkoxy, (C1-6)haloalkoxy, (C1-6)alkoxyalkyl, (C2-6)alkynyl, (C2-6)alkenyl, aryl, heteroaryl, aryloxy, heteroaryloxy, (C3-6)cycloalkyl, carboxy, (C1-6)alkylcarbonyl, arylcarbonyl, (C1-3)haloalkylcarbonyl, (C1-6)alkylcarbonyloxy, (C1-6)haloalkylcarbonyloxy, (C1-6)alkoxycarbonyl, (C1-6)haloalkoxycarbonyl, (C1-6)alkylthiocarbonyl, (C1-6)haloalkylthiocarbonyl, (C1-6)alkoxythiocarbonyl, (C1-6)haloalkoxythiocarbonyl, (C1-6)alkylamino, arylsulfonylamino, arylamino, (C1-6)alkylthio, arylthio, (C2-6)alkenylthio, (C2-6)alkynylthio, (C1-6)alkylsulfinyl, (C2-6)alkenylsulfinyl, (C2-6)alkynylsulfinyl, (C1-6)alkylsulfonyl, (C2-6)alkenylsulfonyl, (C2-6)alkynylsulfonyl, arylsulfonyl, where any of these groups may be non-substituted or substituted with any of the functional groups represented by one more of the following, halogen, hydroxy, cyano, nitro, amino, caboxyl, (C1-6)alkyl, (C1-6)haloalkyl, (C1-6)alkylcarbonyl, (C1-6)alkylcarbonyloxy, (C1-6)haloalkylcarbonyl, (C1-6)haloalkylcarbonyloxy, (C1-6)alkoxy, (C1-6)alkoxycarbonyl, aminocarbonyl, (C1-6)alkylaminocarbonyl, (C1-6)haloalkoxy, (C1-6)haloalkoxycarbonyl, (C1-6)alkylsulfonyl, (C1-6)haloalkylsulfonyl, aryl, heteroaryl and (C3-7)cycloalkyl.
In the definitions given above, unless alkyl, alkenyl and halogen are defined or mentioned, the term alkyl used either alone or in compound words such as xe2x80x9chaloalkylxe2x80x9d or xe2x80x9calkylcarbonylxe2x80x9d includes straight-chain or branched chains containing 1 to 6 carbon atoms. The terms of alkenyl and alkynyl include straight chain or branched alkenes and alkynes respectively containing 2 to 6 carbon atoms, and the term halogen either alone or in the compound words such as haloalkyl indicates fluorine, chlorine, bromine, or iodine. Further a haloalkyl is represented by an alkyl partially or filly substituted with halogen atoms which may be same or different. The term or part of the term xe2x80x9carylxe2x80x9d or xe2x80x9cheteroarylxe2x80x9d are defined as those monocyclic or fused bicyclic aromatic rings wherein at least one ring satisfy the Hxc3xcckel rule and contain 0 to 4 heteroatoms, examples include: phenyl, furyl, furazanyl, thienyl, pyrrolyl, pyrazolyl, oxazolyl, oxadiazolyl, imidazolyl, isoxazolyl, thiazolyl, thiadiazolyl, isothiazolyl, tetrazolyl, pyridinyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, quinolyl, isoquinolyl, quinoxalinyl, benzofuranyl, 2,3-dihydrobenzofuranyl, isobenzofuranyl, benzothienyl, benzodioxolyl, chromanyl, indolinyl, isoindolyl, naphthyl, thienofuranyl and purinyl. These rings can attached through any available carbon or nitrogen, for example, when the aromatic ring system is furyl, it can be 2-furyl or 3-furyl, for pyrrolyl, the aromatic ring system is 1-pyrrolyl, 2-pyrrolyl or 3-pyrrolyl, for naphthyl, the carbobicyclic aromatic ring is 1-naphthyl or 2- naphthyl and for benzofuranyl, the aromatic ring system can be 2-, 3-, 4-, 5-, 6- or 7-benzofuranyl.
The compounds described by the Formula (Ia) and (Ib) can be prepared by the procedures as described herein. Using commercially available starting materials or those whose synthesis is known in the art. the compounds of this invention may be prepared using methods described in the following Schemes, or using modifications thereof which are within the scope of the art. The starting phenol represented by formula II in Scheme 1 can be nitrated according to the literature procedure (WO 9722618). The reaction is accomplished by treatment with nitric acid at a temperature between xe2x88x9230xc2x0 C. and 50xc2x0 C. for 0.5-12 hours. The reaction solution is poured into ice-water, then isolated and purified. IV can be prepared by the reduction of III typically by treatment with iron in an acidic medium such as acetic acid or catalytic hydrogenation at a temperature between 0xc2x0 C. and 50xc2x0 C. for 1-24 hours. IV can be treated with acid chloride or acid anhydride in the presence of base such as trimethyl amine or acid such as pyridinium p-toluensulfonate (PPTS) in an inert solvent such as m-xylene at 20-250xc2x0 C. for 1-24 hours to give benzoxazole type compound represented by formula V. These compounds can be nitrated with a nitration reagent such as nitric acid at a temperature between xe2x88x9210xc2x0 C. and 50xc2x0 C. for 0.5-12 hours. The reaction solution is poured into ice-water followed by filtration. VI can be obtained as a mixture with its regio-isomer represented by formula VII.
The reduction of VI to amine derivatives represented by formula VIII can be carried out by treatment with iron in an acidic medium such as acetic acid or by catalytic hydrogenation at a temperature between 0xc2x0 C. and 30xc2x0 C. for 1-24 hours. Further modification from VIII to IX can be carried out as described in this patent. 
The phthalimide derivative represented by formula XI can be prepared by the treatment of X with phthalic anhydride in an acidic medium such as acetic acid at a temperature between 30xc2x0 C. and 200xc2x0 C. for 1-24 hours.
Nitration can be carried out by its addition to a mixture of sulfuric acid and nitric acid at a temperature between xe2x88x9215xc2x0 C. and 50xc2x0 C. for 0.5-12 hours followed by addition of ice-water to give the desired compound represented by formula XII. XII can be deprotected to give amine derivatives represented by formula XIII. Removal of the protecting group can be accomplished using several methods. such as treatment with hydrazine in a polar solvent such as dimethylsulfoxide (DMSO) or by treatment with an organic amine such as methyl amine in ethanol. Amino group of XIII can be derived to XIV as described in this patent. 
Phthalimide derivative represented by the formula XV in Scheme 3 can be prepared according to the literature procedure (WO 93/14073). Nitration can be carried out by treatment with a nitrating reagent such as nitric acid at a temperature between xe2x88x9230xc2x0 C. and 30xc2x0 C. for 0.5-12 hours. XVI is then converted into the corresponding amine represented by formula XVII by typical reduction procedures e.g. iron in an acidic medium such as acetic acid or by catalytic hydrogenation. Benzoxazole derivatives represented by formula XVIII can be prepared according to the general procedures described in Scheme 1. The phthalimide group can be removed according to the general procedure described in Scheme 2 to give VIII. 
The product represented by formula XXII in Scheme 4 can be prepared analogously by known method (JP2-289573). Urea derivatives represented by formula XX can be prepared by a coupling reaction with the corresponding amine in an inert solvent such as ethyl acetate at a temperature between 0xc2x0 C. and 30xc2x0 C. for 1-12 hours. XXI can be prepared from XX by using diphosgene or related reagent such as triphosgene in an inert solvent such as dichloromethane at a temperature between 0xc2x0 C. and 150xc2x0 C. for 1-12 hours. The final compounds represented by formula XXII can be prepared from XX by treatment with a catalytic amount of base such as sodium methoxide in a polar solvent such as methanol at a temperature between 20xc2x0 C. and 150xc2x0 C. for 0.5-12 hours. 
The product represented by the formula XXIII in Scheme 5 can be prepared analogously by known method (EP 688773). The reaction is carried out at a temperature between xe2x88x9278xc2x0 C. and 100xc2x0 C. for 0.5-24 hours in an inert solvent such as tetrahydrofuran (THF) or toluene. 
The compounds represented by formula XXV in Scheme 6 can be prepared from XXIV by treatment with 2-halo keto-derivatives such as phenacyl bromide in the presence of base such as potassium carbonate in an inert solvent such as acetone or acetonitrile. The reaction can be carried out at a temperature between 30xc2x0 C. and 100xc2x0 C. for 1-24 hours. 
The compounds represented by formula XXVI in Scheme 7 can be prepared according to the procedure outlined by Y. Masuoka et al. in Chem Pharm. Bull 34(1) 130-139 (1986). The starting compound represented by formula XXIV was treated with allyl halide such as methyl 4-bromocrotonate in the presence of base such as sodium bicarbonate in a solvent such as methanol at a temperature between 0xc2x0 C. and 100xc2x0 C. for 1-24 hours 
The product represented by formula XXVII in Scheme 8 can be prepared from XXIV by treatment with 1,2-dicarbonyl derivatives such as methyl pyruvate in an inert solvent such as toluene or THF. The reaction carried out at a temperature between 0xc2x0 C. and 150xc2x0 C. for 0.5-24 hours. 
The product represented by formula XXVIII in Scheme 9 can be prepared from XXIV by a cyclization reaction with 2-halogenated ester such as ethyl 2-bromopropionate. The reaction can be carried out in the presence of base such as potassium carbonate in a solvent such as acetonitrile at a temperature between 25xc2x0 C. and 100xc2x0 C. for 1-24 hours. 
The compounds represented by formula XXVIII in Scheme 10 can be prepared from XXIV using 1,2-dihaloderivatives such as 1,2-dibromoethane in the presence of base such as potassium carbonate in an inert solvent such as acetone. The reaction is carried out at a temperature between 20xc2x0 C. and 150xc2x0 C. for 0.5-24 hours. 
Aniline derivatives represented by formula XXIX in Scheme 11 can be converted to corresponding isocyanates represented by formula XXX, using phosgene or triphosgene in the presence of base such as triethylamine. The reaction can be carried out in an inert solvent such as ethyl acetate at a temperature between 0xc2x0 C. and 100xc2x0 C. for 0.5-24 hours. Uracil derivatives represented by formula XXI can be prepared analogously by known method (U.S. Pat. No. 4,859,229). 
The starting pyrazole derivatives represented by formula XXXII in Scheme 12 can be nitrated with a nitrating reagent such as nitric acid in an acidic medium such as sulfuric acid at a temperature between xe2x88x9230xc2x0 C. and 50xc2x0 C. for 0.5-12 hours. Product (XXXIII) is isolated by addition of water and filtered. XXXIV can be prepared by the reduction of XXXIII typically by catalytic hydrogenation in the presence of catalysts such as palladium on carbon or by treatment with iron in an acidic medium such as acetic acid. Further modification of XXXIV to XXXV is carried out according to the general procedures described in Scheme 1. 
The starting compounds represented by formula XXXVI in Scheme 13 can be prepared analogously by known method (WO97/07104). Nitration can be carried out with a nitrating reagent such as nitric acid in an acidic medium such as sulfuric acid at a temperature between xe2x88x9230xc2x0 C. and 50xc2x0 C. for 0.5-12 hours to give XXXVII. Aniline derivatives represented by formula XXXVIII can be prepared from XXXVII by treatment with iron in an acidic medium such as acetic acid or by catalytic hydrogenation. Further transformation through aminophenol represented by formula XXXIX to XL can be carried out following to the method described in Scheme 1. 
The starting compounds represented by formula XLI in Scheme 14 can be prepared according to the literature procedure (WO97/07104). Nitration can be carried out with a nitrating reagent such as nitric acid. The reaction can be carried out at a temperature between xe2x88x9220xc2x0 C. and 100xc2x0 C. for 0.5-12 hours to give XLII. Aniline derivative represented by formula XLIII can be prepared from XLII by treatment with iron in an acetic medium such as acetic acid or by catalytic hydrogenation. Further transformation through aminophenol represented by formula XLIII to XLIV can be carried out following to the method described in Scheme I 
The starting compound represented by formula XLV in Scheme 15 can be prepared following literature methods, such as U.S. Pat. No. 4,213,773. Nitration can be carried out with a nitrating reagent such as nitric acid with or without acidic medium such as sulfuric acid at a temparature between xe2x88x9220xc2x0 C. and 50xc2x0 C. for 0.5-24 hours to give XLVI. Aminophenol derivatives represented by formula XLVII can be prepared from XLVI by treatment with iron in an acidic medium such as acetic acid or by catalytic hydrogenation. The reaction can be carried out at a temperature between 0xc2x0 C. and 100xc2x0 C. for 1-48 hours. Benzoxazole derivatives represented by formula XLVIII can be prepared according to the general procedures described in Scheme 1. 
The starting compound represented by formula XLIX in Scheme 16 can be prepared following literature method (WO92/06962). Nitration can be carried out with a nitrating reagent such as nitric acid with or without acidic medium such as sulfuric acid at a temperature between xe2x88x9220xc2x0 C. and 50xc2x0 C. for 0.5-24 hours to give L. Aminophenol derivatives represented by formula LI can be prepared from L by treatment with iron in an acidic medium such as glacial acetic acid or by catalytic hydrogenation in the presence of catalyst such as palladium on carbon. The reaction can be carried out at a temperature between 0xc2x0 C. and 100xc2x0 C. for 1-48 hours. Further modification of LI to LII is carried out according to the general procedures described in Scheme 9. 